Dyestuff salt containing heavy metals in complex combination in the acid component



Patented Mar. 19, 1935 a 1 994 7ag UNITED "STATES PATENT orricr DYESTUFF SALT CONTAINING HEAVY METALS IN COMPLEX COMBINATION IN THE-ACID COMPONENT Karl Holzach'. and Fritz Lange, Ludwigshafen-onthe-Rhine, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of'Delaware j No Drawing. Application November 18, 1932, gserzilalsllqo. 643,287. In Germany November 11 Claims. ((1260-12) The present invention relates to improvements chromable triphenylmethane .dyestufis' or hyin dyestufi salts containing heavy metals in comdroxyanthraquinone sulphonic acids with heavy plex combination in the acid component and a metals, such as chromium, copper, cobalt, nickel process of producing same. and iron; generally speaking the chromium com- 5 We have found that coloring materials suitpounds "are most favorable. The chromium and 5 able for coloring masses comprising a substance copper compounds or ortho-hydroxyazo dyestuffs capable of forming films are obtained by causing which contain sulphonic or carboxylic acid groups complexheavy metal compounds of organic dyeare especially suitable. stuffs containing sulphonic or carboxylic acid As suitable dyestuif bases may be mentioned groups to react with organicdyestuff bases with the diphenylmethane and triphenylmethane dye- 10 the formation of salts. The formation of the stuff bases; especially favorable effects are obsalts of the complex heavy metal compounds of tained with triphenylmethane dyestuffs of the organic dyestuffs containing sulphonic or carrhodamine type, for example with rhodamine B boxylic acid groups with organic dyestuif bases is extra, G extra (see Schultz, Farbstofftabellen l5 effected by causing the two components, namely 7thedition, No. 864 and following).

the complex heavy metal dyestuff compounds and The said salts are particularly suitable for the dyestuff bases to react upon one another in coloring masses of thekinddefined above and any suitable manner at ordinary oran elevated solutions thereof, since they are readily soluble in temperature. Usuallytemperatures above 100 the organic solvents commonly used. in the pro- C. are not used. The preparation of the salts is duction' of such masses, such as aliphatic alco- 20 preferably effected in aqueous media whereby the hols or'their' esters, for example ethyl, butyl and two components are usedin a water-soluble form; amyly alcohol, glycol and their esters, ketones, the complex heavy metal compounds are prefersuch as acetone, methylethyl ketone, dibutyl ably employed in the form of their readily waterketone, cyclohexanone and its homologues, and

soluble alkali metalor ammonium salts, but the mixtures of such solvents. For the solvents which 25 free acids may also be employed; the dyestuff may be employed forthe preparation of the colbases are preferably used I in the form of salts, ored compositions in which the said salts are solufor example their salts with hydrochloric acid. ble reference, may be. .had to the solvents de- The salts formed which are difiicultly soluble; in scribed in Cellulose Ester varnishes by Sprex- .water are separated from the aqueous medium. ton, London, 1925, and Natural and Synthetic 30 for example by filtration, and dried; However, the Resins by Barry, Drurnmond and Morrell, Lonformation of the salts may be effected also in ordon, 1926. v ganic solvents whereby-the components are used ,'The following examples .will further illustrate in a form at least partly soluble in the said solhow this inventionmay be carried out in practice vents; for example the complex metal compounds but the invention is not restricted to these exam:- 35

may be used in the form of free acids. The formaples. The parts areby weight. tion of the salts may be effected in the solution of the composition tov be colored itself.- 7

Suitable masses comprising a substance capable 48 parts of rhodamine 13 extra (Schultz, Farb- 40 of forming films are masses consisting of or constofitabellen, 7th edition, No. 864) are dissolved 40 taining cellulose esters or ethers, or artificial or in water and precipitated with an aqueous solunatural resins, including condensation products tion'of 51 parts of the chromium compound of of urea and formaldehyde,and solutions of the the azo dyestuif from diazotized l-nitro-Z-aminoaforementioned materials in organic solvents, phenol-G-sulphonic acid and aceto-acetic acid such as lacquers or' varnishes and the, like. anilide at ordinary or slightly elevated tempera- 5 Especially suitable colored masses may be ob- 'ture. The saltprecipitated is filtered off and tained by starting with cellulose esters orethers. dried. From 2 to 3 parts thereof are dissolved By incorporating the said masses; with the salts in 1000 parts of a commercial nitrocellulose lacin question compositions are obtained which are quer. With the resulting lacquer, bright red especially deeply colored in a great variety of coatings which are very fast to light are produced 50 shades and which are distinguished by an exon metals, paper and other substrata. cellent fastness to light. Suitable complex heavy Similar coatings of somewhat more bluish metal compounds of organic dyestuffs containing shades may be obtained by means of the salt sulphonic or carboxylic acid groups are for ex-- prepared in an analogous manner from 48 parts ample the compounds of chromable azo dyestuffs, of rhodamine B extra and 58 partsof thechro- 55 Example 1 mium compound of the azo dyestufi from diazotized 1-amino-2-naphthol-4-sulphonic acid and 1-phenyl-3-methyl-5-pyrazolone.

Eaample 2 parts of the salt obtained by precipitating 48 parts of rhodamine B extra (see Example 1) in aqueous solution with 29 parts of the copper compound of the azo dyestufi derived from diazotized 4-chlor-2-aminophenol-6-sulphonic and 2-amino-5-naphthol-7-sulphonic acid (coupled in alkaline solution) are dissolved in 1000 parts of a commercial nitrocellulose lacquer. The resulting lacquer yields bright violet red coatings, very fast to light, on a great variety of substrata.

Example 3 Example 4 90 parts of Rhoduline blue 6 G (Schultz, Farbstofitabellen, 7th edition, N0. 755) are precipitated in aqueous solutionwith 51 parts of the chromium compound of the azo dyestuff derived from diazotized 4-nitro-2-aminophenol-6-sulphonic acid and aceto-acetic acid anilide. The salt formed is filtered off and dried. 3 parts thereof are dissolved in 1000 parts-of a commercial nitrocellulose lacquer. Blue green coatings of very good 'fastness to light are .obtained with there- -sulting lacquer.

Example '5 2 parts of the salt prepared from .90 parts of Rhoduline blue 6 G and 61 parts of the chromium compound of Chromazurol S (Schultz, .Farbstoiftabellen, 5th edition, No..,.554) in an analogous manner as described in Example 1 are dissolved in 1000 parts of a commercial nitrocellulose lacquer. Pale blue coatings of good fastness to light are obtained. with the resulting lacquer.

Example -6 36 parts of auramine G (Schultz, Farbstofftabellen; 7th edition (1931), No. 753) dissolved in water are precipitated with an aqueous solution of 51 parts of the chromium compound of the azo dyestu-ff obtainable 'by'coupling diazotized 4-nitro- 2-aminophenol-6-sulphonic acid with aceto-acetic acid anilide. The salt thus obtained is filtered oil and dried. 5 parts thereof aredissolved in- 1000 parts of a commercial nitrocellulose lacquer. The resulting lacquer yields vivid yellow coatings of good fastness' to light, on a substrata.

What We claim is: 1. The process of producing coloring materials, which comprises causing a complex heavy metal compound of an organic dyestu-ff selected from great variety of the group consisting of ortho-hydroxyazo-dyestuiTs, polyarylmethane dyestuffs and hydroxy anacid thraquinone sulphonic acids capable of forming complex heavy metal compounds and containing at least one substituent selected from thegroup 7 consisting of the sulphonic and carboxylic acid groups to react with a base "of a polyarylmethane dyestufi free from groups capable of forming complex heavy metal compounds with the formation of a salt.

2. The processoi producing coloring materials which, comprises causing a complex chromium compound of an organic dyestuff selected from the group consisting of 'ortho-hydroxyazo-dyestufis,

polyarylme'thane'dyestuffs andhydroxy anthra'quinone sulphonic acids capable of forming complex chromium compounds and containing at least one substituent selected from the group consisting of the'sulphonic and carboxylic acid groups to react with a base of apolyarylmethane dyestufi free from groups capable of forming complex heavy metal compounds with the formation of a salt.

3. The process of producingcoloring materials, which comprises causing a complex heavy. metal compound .of an ortho-hydroxyazodyestufl :containing at least one substituent selected fromcthe group consisting of sulphonic and-carboxylic acid 225.

groups to react with a base of apolyarylmethane dyestufi free from groups capablerof forming complex heavy metal compounds with the formation ofasalt. l.

4. The process of producing-coloring materials, which comprises causing a. complex chromium compound of an ortho-hydroxyazo-dyestuff containing at least one substituent selected from the group consisting-of the sulphonic and carboxylic acid groups to reactwith a base ofa polyarylmethane dyestuif free from groups capable of forming complex heavy metal compounds with the formation of a-salt.

5. The process of producing-coloring materials which comprises causing 'a complexchromium compound of an ortho-hydroxyazo-dyestuff 1 com taining atleast'onesubstituent selected from the group consisting of the sulphonicand carboxylic.

acid groups to react with the base of a triphenylmethane dyestufi free from groups capable of forming complexheavy metal'compounds with'the formation of a salt.

6. A salt of a complexof an organic dyestuff selected from the group consisting of "ortho-hydroxyazo dyestuffs, polyarylmethane dyestuffs and hydroxyanthra'quinone sulphonic acids'cap'able-of forming complex heavy metal compounds and containing at least one sub- "stituentselected from theigroup consisting of the sulphonic and carboxylic acid groups with, a

heavy metal compound I base of' a polyarylmethane dyestufi free from 1 groups capable of forming complex heavy metal 7 compounds.

7. A salt of a complex chromium compound I of an'organ-ic dyestufi selected from the group consisting of ortho-hydroxyazodyestuffs, poly-.-

arylmethane dyestuifs andhydroxy anthraquinone sulphonic acids capable of forming complex chromium compounds and containing atleast onefsubstituent selected from the group consisting of the sulphonic and the carboxylic acid groupswith a base of a polyarylmethane dyestufi free from groups capable of forming complex heavymetal compounds. 1 v

8. A salt of a complex chromium compound of an ortho-hydroxyazo-dyestufi containing at least one substituent selected from the group consisting of the sulphonic and carboxylic acid groups with the base of a .triphenylmethane, dyestuff free from groups capable of forming complex heavy metal compounds.

9. The salt of rhodamine B extra with the complex chromium compound of the azo dyestuff from diazotized 4-nitro-2-aminophenol-6-sulphonic acid and aceto-acetic acid anilide, coloring nitrocellulose lacquer bright red shades of excellent fastness to light.

10. The salt of rhodamine B extra with the complex chromium compound of the azo dyestufi from diazotized l-amino-2-naphthol-4-sulphonic acid and 1-pheny1-3-methyl-5-pyrazolone, coloring nitrocellulose lacquer bright bluish red shades of excellent fastness to light.

11. The salt of rhodamine B extra with the complex chromium compound of the azo dyestufi from diazotized 4-nitro-2-aminophenol-6-sulphonic acid and 1-phenyl-3-methyl-5-pyrazolone, coloring celluloid red shades of excellent fastness to light.

KARL HOLZACH. FRITZ LANGE. 

